This grant from the Organic Dynamics Program supports the work of Professor Robert D. Bach at Wayne State University to study the structures and reactivities of alkyl peroxides, metal hydroperoxides, peroxy acids, dioxiranes, and carbonyl oxides by high level ab initio methods. Specifically, the oxygen atom transfer from peroxyformic acid, dioxirane, carbonyl oxide, peroxide, and vanadium peracid to ethylene and other molecules like ammonia, phosphine, and sulfides will be analyzed. Emphasis is given to the solvent and substituent effects on these transitions and their influence on the biradical states and isomerizations. The study will address the Sharpless epoxidation. %%% In this project Dr. Robert Bach will conduct computational studies to address fundamental aspects on oxidation reactions. His high level ab initio approach aims to provide insight into the structures, electronic properties, and solvent effects on the oxygen atom transfer reactivities of alkyl peroxides, metal hydroxyperoxides, peroxyacids, dioxiranes, and carbonyl oxides. These studies aim to advance the understanding of metal catalyzed oxidations that are ubiquitous in industry, organic synthesis, and biochemistry and may lead to more environmental benign processes.
